KR20180089850A - Thermo electric sintered body and thermo electric element - Google Patents

Abstract

According to an embodiment of the present invention, a thermoelectric sintered body comprises thermoelectric powder which includes a plurality of first powder in a shape of plate-type flakes arranged in a horizontal direction and a plurality of second powder in a shape different from that of the first powder, wherein the second powder is included by 5 vol% of the total thermoelectric powder.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoelectrically-sintered body and a thermoelectric element,

Embodiments relate to a thermoelectric element and a thermoelectric element.

Thermoelectric phenomenon is a phenomenon caused by the movement of electrons and holes inside a material, which means direct energy conversion between heat and electricity.

Thermoelectric elements are collectively referred to as elements utilizing thermoelectric phenomenon and have a structure in which a p-type thermoelectric material and an n-type thermoelectric material are bonded between metal electrodes to form a PN junction pair.

The thermoelectric element can be classified into a device using a temperature change of electrical resistance, a device using a Seebeck effect that generates electromotive force by a temperature difference, a device using a Peltier effect that is a phenomenon in which heat is generated by heat or a heat is generated .

Thermoelectric devices are widely applied to household appliances, electronic components, and communication components. For example, a thermoelectric element can be applied to a cooling device, a heating device, a power generation device, and the like. As a result, there is a growing demand for thermoelectric performance of thermoelectric elements.

This thermoelectric performance is related to the thermoelectric element constituting the thermoelectric element, and more specifically, to the thermoelectric element constituting the thermoelectric element.

Therefore, there is a demand for the production of a thermoelectric sintered body capable of improving the thermoelectric performance.

The embodiments are intended to provide thermoelectric elements and thermoelectric elements having improved uniformity and efficiency.

The thermoelectric element according to the embodiment includes a thermoelectric powder, and the thermoelectric powder includes a plurality of first powders arranged in a horizontal direction and in the form of plate-like blades; And a plurality of second powders different in shape from the first powders, wherein the second powders contain no more than 5 vol% with respect to the entire thermoelectric powder.

The thermoelectric-powder sintered body manufactured by the apparatus for manufacturing a thermoelectric-power-receiving sintered body according to the embodiment can arrange the powder of the thermoelectric-powder sintered body in most one direction. That is, the arrangement of the powders can be arranged in one direction in the horizontal direction.

Accordingly, the thermal conductivity of the thermoelectric sintered body can be reduced and the electrical conductivity can be improved. Accordingly, the thermoelectric performance of the thermoelectric leg can be improved when the thermoelectric sintered body is applied to the thermoelectric leg of the thermoelectric device.

In addition, since the ball-shaped thermoelectric powder that causes a decrease in the electrical conductivity in the thermoelectric powder control part can be reduced, the thermoelectric performance of the thermoelectric leg can be improved.

FIG. 1 is a view showing an apparatus for manufacturing a thermo-sintered body according to an embodiment.
2 is a cross-sectional view of a control region of an apparatus for producing a thermo-sintered body according to an embodiment.
3 is a view showing the shape of the second powder according to the embodiment.
4 is a view showing a photograph of the shape of the second powder according to the embodiment.
5 is a diagram showing a thermoelectric powder mixed with the first and second powders.
6 is a photograph showing a thermoelectric powder mixed with the first and second powders.
7 is a diagram showing a particle diameter distribution of the first powder according to the embodiment.
8 is a view showing a structure in which thermoelectric powders are disposed in a mold member in the thermoelectric-component producing apparatus according to the embodiment.
FIG. 9 is a photograph showing a scanning electron microscope (SEM) photograph of a thermoelectric sintered body manufactured by the thermoelectric-component producing apparatus according to the embodiment.
10 is a perspective view of a thermoelectric element including a thermo-sintered body according to an embodiment.
11 is a cross-sectional view of a thermoelectric element including a thermo-sintered body according to an embodiment.
12 is a sectional view showing one embodiment of the thermoelectric leg according to the embodiment.

The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated and described in the drawings. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terms including ordinal, such as second, first, etc., may be used to describe various elements, but the elements are not limited to these terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the second component may be referred to as a first component, and similarly, the first component may also be referred to as a second component. And / or < / RTI > includes any combination of a plurality of related listed items or any of a plurality of related listed items.

It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, . On the other hand, when an element is referred to as being "directly connected" or "directly connected" to another element, it should be understood that there are no other elements in between.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings, wherein like or corresponding elements are denoted by the same reference numerals, and redundant description thereof will be omitted.

Hereinafter, an apparatus for manufacturing a thermo-sintered body according to an embodiment will be described with reference to Figs. 1 and 2. Fig.

Referring to FIGS. 1 and 2, the apparatus for manufacturing a thermoelectric body according to an embodiment of the present invention may include a powder control unit 1000 and a powder sintered body 2000.

The powder control unit 1000 may be a thermoelectric powder control device. The powder sintered body 2000 may be a thermoelectric powder sintering apparatus.

The powder controller 1000 and the powder sintered body 2000 may be connected to each other. In detail, the particle size and concentration of the powder are controlled in the powder controller 1000, and the controlled powder can be moved to the powder sintered body 2000 and sintered.

The powder control unit 1000 and the powder sintered body 2000 may be detachably connected to each other. For example, the powder control part 1000 and the powder sintered part 2000 may be used as respective independent devices, or the powder control part 1000 and the powder sintered part 2000 may be combined with each other, .

The powder controller 1000 may include a plurality of regions. For example, the powder control unit 1000 may include an input area 1A, a control area 2A, and a supply area 3A. remind

A thermoelectric powder may be provided in the charging area 1A. For example, the thermoelectric powder may be a powder for producing a thermoelectric leg of a thermoelectric element.

For example, the thermoelectric powders may be milled together with an additive for doping. For example, ribbon-shaped powders and additives for doping can be mixed by using a super mixer, a ball mill, an attrition mill, a three-roll mill, or the like .

The thermoelectric powder may include Bi, Te and Se. Further, the doping additive may include Cu and Bi2O3. At this time, the thermoelectric material including Bi, Te and Se contains 99.4 to 99.98 wt% of Cu, 0.01 to 0.1 wt% of Cu, and Bi2O3 of 0.01 to 0.5 wt%, preferably Bi, Te and Se The thermoelectric material containing 99.47 to 99.98 wt% of thermoelectric material, 0.01 to 0.07 wt% of Cu, and 0.01 to 0.45 wt% of Bi2O3, more preferably 99.67 to 99.98 wt% of thermoelectric material containing Bi, Te and Se, Is added in a composition ratio of 0.01 to 0.03 wt%, and Bi2O3 is added in a composition ratio of 0.01 to 0.30 wt%, and then milled.

The input area 1A and the control area 2A can be separated from each other. In detail, a gate 1100 is disposed between the input region 1A and the control region 2A, and the input region 1A and the control region 2A can be separated from each other by the gate 1100 have.

The gate 1100 may be opened or closed through an external control unit 3000. In detail, when the thermoelectric powder is input into the input region 1A, the gate 1100 is kept closed, whereby the input region 1A and the control region 2A can be separated from each other.

Next, after the thermoelectric powder is completely charged into the charging region 1A, the gate 1100 can be opened through the control unit 3000. FIG. That is, the thermoelectric powder injected into the input region 1A can move toward the control region 2A as the gate 1100 is opened.

Referring to FIG. 2, the control area 2A may include a first area 1A ', a second area 2A', and a third area 3A '.

The first 'region 1A', the second 'region 2A' and the third 'region 3A' may be arranged in a layered structure. In detail, the second region 2A 'may be disposed on the third region 3A', and the first region 1A 'may be disposed on the second region 2A' . That is, the second region 2A 'may be disposed between the first region 1A' and the third region 3A '.

The first filter portion F1 may be disposed between the first region 1A 'and the second region 2A'. In addition, a second filter unit F2 may be disposed between the second region 2A 'and the third region 3A'.

The first filter unit F1 and the second filter unit F2 may include a plurality of holes. For example, the first filter unit F1 may include first holes H1. In addition, the second filter unit F2 may include second holes H2.

The first hole (H1) and the second hole (H2) may have different sizes. In detail, the size of the first hole (H1) may be smaller than the size of the second hole (H2). That is, the size of the second hole H2 may be larger than the size of the first hole H1.

The size of the first hole (H1) and the second hole (H2) can be controlled to an appropriate size for separating the thermoelectric powder containing powder having different particle size and shape. For example, the size of the first hole H1 and the second hole H2 may be smaller than the size of the first powder described below, and may be larger than the size of the second powder.

For example, the size of the first hole H1 may be about 1100 탆 or more. More specifically, the size of the first hole H1 may be about 1100 탆 to about 1500 탆. The size of the second hole H2 may be about 1500 mu m or more. In detail, the size of the second hole H2 may be about 1500 μm to 2000 μm.

In addition, the vibration section 1200 may be disposed in the second region 2A '. The vibration unit 1200 may transmit the vibration applied by the external control member 3000 to the first filter unit F1 and the second filter unit F2.

The vibration unit 1200 may be formed in a spherical shape, a bar shape, or a polygonal shape. For example, the vibration unit 1200 may include a spherical silicon ball or the like.

The thermoelectric powder injected through the input region 1A may be transferred to the first region 1A '. The powder input through the input region 1A may include the first powder P1 and the second powder P2.

In detail, the thermoelectric powders injected through the input region 1A may include a first powder P1 and a second powder P2 having different shapes from each other. In detail, the first powder (P1) may be formed into a ribbon shape, that is, a flaky flake shape. Here, the flaky flake shape may have a major axis and a minor axis. In detail, the flake shape may have different lengths on the major and minor axes. In detail, the ratio of the major axis to the minor axis of the flaky flake shape may be 1: 1.2 to 1: 6. More specifically, the ratio of the major axis to the minor axis of the flaky flake shape may be 1: 1.2 to 1: 2.5.

In addition, the second powder P2 may be formed in a shape different from the plate-like blade shape. For example, the second powder P2 may have a spherical shape, i.e., a ball shape, as shown in FIGS.

The thermoelectric powder can be subjected to a rapid solidification process during its production. By this cooling process, the thermoelectric powder has the same composition and composition as the thermoelectric powder of the flaky flakes, which are not flaky flakes, Powder can be produced.

As shown in detail in FIGS. 5 and 6, a thermoelectric powder mixed with a plurality of unit powders having the same composition and composition ratio but having different shapes can be produced.

The thermoelectric powders of the plate-shaped blake shape and the thermoelectric powders of the plate-like blake shape have different lattice constants and the thermoelectric powders of the shape different from the shape of the plate-shaped blades and the plate-shaped blades are sintered together The thermoelectric performance of the thermoselective body may be deteriorated due to an increase in resistance or the like.

Thus, the first powder P1 and the second powder P2 are filtered in the second region 2A of the powder controller 1000 to remove all or most of the second powder P2, The powder can be transferred to the powder sintered body 2000. That is, most of the thermoelectric powder transferred to the powder sintered body 2000 may be the first powder P1.

As described above, the shape of the first powder P1 and the shape of the second powder P2 may be different. That is, the particle diameters of the first powder P1 and the second powder P2 may be different. In detail, the particle diameter of the first powder (P1) may be larger than the particle diameter of the second powder (P2). In detail, the first powder P1 may be formed in a plate-like blade shape, and the second powder P2 may be formed in a ball shape.

In addition, the particle size of the second powder P2 may be about 300 [mu] m to about 1100 [mu] m. Also, the average particle size of the second powder P2 may be about 650um to about 670um. 7, the second powder P2 has a particle diameter ranging from about 300 .mu.m to about 1100 .mu.m, and the second powder P2 having a particle diameter ranging from about 650 .mu.m to about 670 .mu.m has the largest particle diameter It can contain a large amount.

The first filter portion F1 disposed between the first region 1A 'and the second' region 2A 'separates the first powder P1 and the second powder P2 . That is, the second powder P2 having a relatively small particle diameter is moved to the second region 2A 'through the hole through the hole of the first filter portion F1, and the first powder P1 May remain in the first region 1A '.

In detail, vibration can be applied to the powder control unit 1000 through the external control member 3000. In detail, the vibration member 1500 can be operated by the control member 3000, and vibration can be applied to the control region 2A by the vibration member 1500. That is, the vibration member 1500 can apply the vibration to the first 'region 1A', the second 'region 2A' and the third 'region 3A'.

The vibration applied to the control region 2A is transmitted to the vibration unit 1200 and the vibration unit 1200 moves upward and downward and the first powder P1 and the second powder P2 , It is possible to apply the vibration to the first filter unit F1. Specifically, vibration may be applied to the first filter unit F1 at a first frequency.

The first powder P1 and the second powder P2 are moved in the vertical direction by the vibration of the first frequency and are transmitted through the first filter P1 to the first powder P1, Can be left in the first region 1A 'and only the second powder P2 can be moved to the second region 2A'.

The second filter portion F2 may move the second powder P2 moved to the second 'region 2A' to the third 'region 3A'.

The control unit 3000 applies vibration to the powder control unit 1000 and operates the vibration member 1500 by the control member 3000 so that the vibrating member 1500 moves the control member 3000, It is possible to apply vibration to the substrate 2A. The vibration applied to the control region 2A is transmitted to the vibration unit 1200 and the vibration unit 1200 moves upward and downward and the first powder P1 and the second powder P2 , It is possible to apply the vibration to the second filter unit F2. In detail, vibration may be applied to the second filter unit F2 at a second frequency. At this time, the second frequency may be larger than the first frequency.

The second powder P2 is transferred from the second region 2A 'to the third region 3A' and the second powder P2 is transferred from the third region 3A 'to the third region 3A' ). ≪ / RTI > The second powder P2 collected in the third region 3A 'may be exhausted through the outside.

In addition, the first powder P1 remaining in the first region 1A 'may be pulverized by the second vibration of the second frequency magnitude. Accordingly, the overall particle size uniformity of the first powder (P1) can be improved.

The pulverized and powdered powder in the control region 2A can be moved to the supply region 3A. In detail, the first powders P1 of the first region 1A 'of the control region 2A can be moved to the supply region 3A.

That is, in the control region 2A, the shape and particle diameter of the powder injected in the input region 1A can be controlled. Specifically, the shape of the thermoelectric powder can be filtered by the first powder having a plate-like blade shape by the control region 2A, and the particle size uniformity of the plate-like blade shape can be improved.

In detail, the second powder, that is, the ball-shaped thermoelectric powder, which causes a decrease in the electrical conductivity in the thermoelectric powder through the first filter portion and the second filter portion, can be removed, The shape uniformity of the sintered body can be improved and the thermoelectric characteristics of the sintered body to be sintered can be improved. That is, the second powder having a shape and a lattice constant different from that of the first powder may affect the arrangement of the first powder, and thus cracks may be generated inside the finally produced thermoelectric element, or voids So that the electrical conductivity of the P-type thermoelectric leg and the N-type thermoelectric leg produced by the thermoelectric sintered body can be reduced.

At this time, the voids of the thermoelectric element produced by the thermoelectric powder according to the embodiment may be about 5% or less with respect to the total area of the thermoelectric element.

However, by minimizing the second powder having different shape and lattice constant from that of the first powder, the thermoelectric sintered body according to the embodiment can minimize the decrease in the electrical conductivity by the second powder and improve the thermoelectric characteristics of the thermoelectric leg .

In addition, since the first powder can be pulverized to a predetermined size through the vibration applied to the control region, the grain size uniformity of the first powder can be improved.

In the powder sintered body 2000, powders filtered or pulverized by the powder controller 1000 may be moved.

In detail, the powder sintered body 2000 may be formed by sintering powders squeezed or pulverized by the powder control unit 1000.

The powder sintered body 2000 may include a collecting member 2100, a seive member 2200, a mold member 2300, and a driving member 2400.

The collecting member 2100 may be sifted or pulverized powders may be moved in the powder control unit 1000. In detail, the powder that has been filtered and pulverized in the control region 2A of the powder control unit 1000 can be moved to the collecting member 2100 of the powder sintered body 2000 through the supply region.

That is, the powder to be transferred to the collecting member 2100 may be the first powder (P1), that is, the thermal powder having a plate-like blade shape. That is, the powder transferred to the collecting member 2100 may include the second powder P2, that is, the thermoelectric powder from which the ball-shaped thermoelectric powder causing the decrease in electric conductivity is removed.

Powder transferred to the collecting member 2100 may be transferred to the sieve member 2200. The sieve member 2200 may include a plurality of sieve portions. In detail, the sieve member 2200 may include a first sieve portion 2210, a second sieve portion 2220, a third sieve portion 2230, and a fourth sieve portion 2240.

The first cervical portion 2210, the second cervical portion 2220, the third cervical portion 2230 and the fourth cervical portion 2240 may be formed in a mesh shape. The first sipe portion 2210, the second sipe portion 2220, the third sipe portion 2230, and the fourth sipe portion 2240 may be formed by a mesh line and a mesh line formed by the mesh line, . ≪ / RTI >

The sizes of the mesh openings of the first sipe portion 2210, the second sipe portion 2220, the third sipe portion 2230 and the fourth sipe portion 2240 may be varied depending on the particle size and shape of the powder Can be changed.

The powder of the collecting member 2100 can be moved to the mold member 2300 through the sieve member 2200. [ The sieve member 2200 may control the directionality of the powder moving to the mold member 2300.

In detail, the sieve member 2200 can control the ribbon shape, that is, the flake shape powder, to be arranged in the mold member 2300 in one direction.

Referring to FIGS. 8 and 9, the first powders P1 may be arranged in a first direction in a receiving part, that is, inside the mold member 2300. As shown in FIG. That is, the first powders (P1) may be arranged in the horizontal direction inside the mold member (2300). That is, most of the first powders P1 disposed in the mold member 2300 are horizontally disposed, and the mold member 2300 can be filled.

In this case, the horizontal direction may be a direction having a vertical component with reference to the direction of gravity, and the horizontal direction may be a direction perpendicular to a virtual vertical line in the gravity direction, The inclination direction may be included up to the direction.

That is, the horizontal direction may be defined as a direction having a horizontal component with the bottom surface of the receiving part, that is, the bottom surface of the mold member 2300, and a direction inclining at an angle of within ± 15 degrees with respect to the bottom surface.

For example, the first powder disposed in the horizontal direction within the mold member 2300 may be about 95% by volume or more based on the entire first powder. In detail, the first powder disposed in the horizontal direction inside the mold member 2300 may be about 95% by volume to about 100% by volume of the entire first powder. More specifically, the first powder disposed in the horizontal direction within the mold member 2300 may be about 96% by volume to about 99% by volume of the entire first powder.

Then, the mold member 2300 may be sintered through the driving member 2400 or the like. In detail, the driving member 2400 may include a rotation unit 2410, a motor unit 2420, and a pressure unit 2430, and the mold member 2300 may be rotated by the driving member 2400, .

For example, the mold member 2300 may be sintered at a temperature of about 400 ° C. to about 550 ° C., about 35 MPa to about 60 MPa for about 1 minute to about 30 minutes using a spark plasma sintering (SPS) Can be sintered for about 1 minute to about 60 minutes at about 400 ° C to about 550 ° C, about 180 MPa to about 250 MPa, using a hot-press machine.

The thermoelectric sintered body thus manufactured is cut through a cutting process, and a thermoelectric leg which is finally applied to the thermoelectric element can be manufactured.

8 and 9, SEM photographs of the sintered body of the pre-fired powder sintered by the sintering machine according to the embodiment are shown.

Referring to FIGS. 8 and 9, it can be seen that the arrangement of the powders of the thermoelectric-powder sintered body is mostly arranged in one direction. That is, it can be seen that the powders are arranged in one direction in the horizontal direction. At this time, the powder of the sintered body may mean a crystal grain after sintering.

Accordingly, the thermal conductivity of the thermoelectric sintered body can be reduced and the electrical conductivity can be improved. Accordingly, the thermoelectric performance of the thermoelectric leg can be improved when the thermoelectric sintered body is applied to the thermoelectric leg of the thermoelectric device.

In addition, since the amount of the second powder, that is, the powder having a shape different from that of the plate-shaped blades, can be reduced in the thermoelectric powder control part, the thermoelectric performance of the thermoelectric leg after thermoelectric sintering can be improved . In detail, the second powder that causes a decrease in electric conductivity in the thermoelectric-powder sintered body may be about 5 vol% or less with respect to the total powder. More specifically, the second powder that causes a decrease in the electrical conductivity in the thermoelectric-powder sintered body may be about 3 vol% or less with respect to the total powder. More specifically, the second powder that causes a decrease in the electrical conductivity in the thermoelectric-powder sintered body may be about 1 vol% or less with respect to the total powder

Hereinafter, the present invention will be described in more detail with reference to the method for producing thermoelectric powders according to Examples and Comparative Examples. These embodiments are merely illustrative of the present invention in order to explain the present invention in more detail. Therefore, the present invention is not limited to these embodiments.

Example  One

The thermoelectric material was heat-treated to produce an ingot. The ingot was pulverized and sieved to obtain a thermoelectric powder.

Subsequently, the sintered body was sintered, and the p-type thermoelectric leg and the n-type thermoelectric leg were prepared by cutting the sintered body.

At this time, the powder for the thermoelectric legs contained 0.1 vol% of the ball-like powder together with the powder of the plate-like blade shape.

Then, the electrical conductivity of the P-type thermoelectric leg and the N-type thermoelectric leg was measured.

Example  2

Similar to Example 1 except that the ball-shaped powder includes a plate-shaped blade-like powder and a ball-shaped powder, and the ball-shaped powder contained about 0.5 volume% After the P-type thermoelectric leg and the N-type thermoelectric leg were manufactured, the electric conductivity of the P-type thermoelectric leg and the N-type thermoelectric leg was measured.

Example  3

The P-type thermoelectric leg and the N-type thermoelectric leg were manufactured in the same manner as in Example 1, except that the ball-shaped powder contained about 1.0% by volume with respect to the entire thermoelectric leg powder, The electrical conductivity of the N type thermoelectric leg was measured.

Example  4

The P type thermoelectric leg and the N type thermoelectric leg were manufactured in the same manner as in Example 1 except that the ball powder contained about 2.0 vol% The electrical conductivity of the N type thermoelectric leg was measured.

Example  5

The P-type thermoelectric leg and the N-type thermoelectric leg were prepared in the same manner as in Example 1, except that the ball-shaped powder was contained in an amount of about 3.0% by volume based on the total thermo-legable powder. The electrical conductivity of the N type thermoelectric leg was measured.

Example  6

The P type thermoelectric leg and the N type thermoelectric leg were manufactured in the same manner as in Example 1 except that the ball powder contained about 4.0 vol% The electrical conductivity of the N type thermoelectric leg was measured.

Example  7

The P-type thermoelectric leg and the N-type thermoelectric leg were manufactured in the same manner as in Example 1, except that the ball powder contained about 5.0% by volume of the powder for the entire thermo leg, The electrical conductivity of the N type thermoelectric leg was measured.

Example  8

The P-type thermoelectric leg and the N-type thermoelectric leg were manufactured in the same manner as in Example 1, except that the ball powder contained about 6.0% by volume of the powder for the entire thermoelectric leg, The electrical conductivity of the N type thermoelectric leg was measured.

Comparative Example

An ingot was prepared by heat treatment of the thermoelectric material, and the ingot was pulverized and the thermoelectric leg powder was obtained without sieving.

The P-type thermoelectric leg and the N-type thermoelectric leg were prepared in the same manner as in Example 1, and the P-type thermoelectric leg and the N Type thermoelectrons were measured.

P-type thermoelectric leg electrical conductivity (S / cm) N-type thermoelectric leg electrical conductivity (S / cm) Example 1 1106 806 Example 2 1106 806 Example 3 1101 803 Example 4 1092 792 Example 5 1077 770 Example 6 1063 764 Example 7 1041 759 Example 8 989 712 Comparative Example 920 677

Referring to Table 1, it can be seen that the thermoelectric legs according to Examples 2 to 6 have a smaller electric conductivity difference than the thermoelectric legs according to Example 1, that is, thermoelectric legs containing minute amounts of ball powder.

That is, it can be seen that the thermoelectric leg including 0.1 to 6.0 vol% of ball-shaped powder has a slight difference in electric conductivity within about 5% as compared with the thermoelectric leg including a minute amount of ball-shaped powder.

However, it can be seen that the thermoelectric legs according to Examples 7, 8 and Comparative Example have a larger electric conductivity difference than the thermoelectric legs according to Example 1, that is, thermoelectric legs containing a small amount of ball powder.

That is, it can be seen that the thermoelectric leg including the ball powder at 5.0 vol% or more has a large electric conductivity difference of about 5% or more as compared with the thermoelectric leg without the ball powder.

That is, the ball-like powders according to Examples 7 and 8 and Comparative Example were mixed together with the powder of plate-like blades to form voids or cracks in the sintered body, whereby the electrical conductivity of the thermoelectric legs to be produced was greatly reduced .

10 to 12, an example of a thermoelectric element to which a thermoselective element manufactured by the thermoelectric-thermistor manufacturing apparatus according to the embodiment is applied will be described.

10 to 12, a thermoelectric element 100 includes a lower substrate 110, a lower electrode 120, a P-type thermoelectric leg 130, an N-type thermoelectric leg 140, an upper electrode 150, And may include a substrate 160.

The lower electrode 120 may be disposed between the lower substrate 110 and the lower surface of the P-type thermoelectric leg 130 and the N-type thermoelectric leg 140. The upper electrode 150 may be disposed between the upper substrate 160 and the upper bottom surface of the P-type thermoelectric leg 130 and the N-type thermoelectric leg 140.

Accordingly, the plurality of P-type thermoelectric legs 130 and the plurality of N-type thermoelectric legs 140 may be electrically connected by the lower electrode 120 and the upper electrode 150. A pair of P-type thermoelectric legs 130 and N-type thermoelectric legs 140, which are disposed between the lower electrode 120 and the upper electrode 150 and are electrically connected to each other, may form a unit cell.

For example, when a voltage is applied to the lower electrode 120 and the upper electrode 150 through the lead wires 181 and 182, the P-type thermoelectric conversion element 130 is turned off from the N-type thermoelectric leg 130 The substrate on which current flows through the N-type thermoelectric legs 140 to the P-type thermoelectric legs 130 can be heated to act as a heat generating portion.

Here, the P-type thermoelectric leg 130 and the N-type thermoelectric leg 140 may be bismuth telluride (Bi-Te) thermoelectric legs containing bismuth (Bi) and tellurium (Ti) as main raw materials.

The P-type thermoelectric leg 130 may be formed of a material selected from the group consisting of Sb, Ni, Al, Cu, Ag, Pb, B, 99 to 99.999% by weight of a bismuth telluride (Bi-Te) base material containing at least one of gallium (Ga), tellurium (Te), bismuth (Bi) and indium It may be a thermoelectric leg comprising from 0.001 wt% to 1 wt% of the mixture. For example, the base material may be Bi-Sb-Te and Bi or Te in an amount of 0.001 wt% to 1 wt% of the total weight.

The n-type thermoelectric transducer 140 may be formed of at least one selected from the group consisting of Se, Ni, Al, Cu, Ag, Pb, B, 99 to 99.999% by weight of a bismuth telluride (Bi-Te) base material containing at least one of gallium (Ga), tellurium (Te), bismuth (Bi) and indium It may be a thermoelectric leg comprising from 0.001 wt% to 1 wt% of the mixture. For example, the base material may be Bi-Se-Te and further contain Bi or Te in an amount of 0.001 wt% to 1 wt% of the total weight.

The P-type thermoelectric leg 130 and the N-type thermoelectric leg 140 may be formed in a bulk or laminated form. Generally, the bulk type P-type thermoelectric leg 130 or the bulk N-type thermoelectric leg 140 is manufactured by heat-treating the thermoelectric material to produce an ingot, pulverizing and sieving the ingot to obtain a thermoelectric leg powder, Sintered body, and cutting the sintered body. The laminated P-type thermoelectric leg 130 or the laminated N-type thermoelectric leg 140 is formed by applying a paste containing a thermoelectric material on a sheet-shaped substrate to form a unit member, then stacking and cutting the unit member Can be obtained.

12, at least one thermoelectric leg 700 of the P-type thermoelectric leg 130 and the N-type thermoelectric leg 140 according to the embodiment includes a thermoelectric material layer 710, a thermoelectric material layer 710, A first metal layer 760 and a second metal layer 770 respectively disposed on one surface of the thermoelectric material layer 710 and the other surface opposite to the surface, a first metal layer 760 and a second metal layer 770 disposed between the thermoelectric material layer 710 and the first metal layer 760, A second bonding layer 750 disposed between the bonding layer 740 and the thermoelectric material layer 710 and the second metal layer 770 and a second bonding layer 750 disposed between the first metal layer 760 and the first bonding layer 740 And a second plating layer 730 disposed between the first plating layer 720 and the second metal layer 770 and the second bonding layer 750. At this time, the thermoelectric material layer 710 and the first bonding layer 740 are in direct contact with each other, and the thermoelectric material layer 710 and the second bonding layer 750 are in direct contact with each other. The first bonding layer 740 and the first plating layer 720 are in direct contact with each other and the second bonding layer 750 and the second plating layer 730 are in direct contact with each other. The first plating layer 720 and the first metal layer 760 are in direct contact with each other and the second plating layer 730 and the second metal layer 770 are in direct contact with each other.

The thermoelectric material layer 710 may include bismuth (Bi) and tellurium (Te) which are semiconductor materials. The thermoelectric material layer 710 may have the same material or shape as the P-type thermoelectric leg 130 or the N-type thermoelectric leg 140.

The first metal layer 760 and the second metal layer 770 may be selected from copper (Cu), copper alloy, aluminum (Al), and aluminum alloy, and may have a thickness of 0.1 to 0.5 mm, preferably 0.2 to 0.3 mm Thickness.

The first plating layer 720 and the second plating layer 730 may each contain at least one of Ni, Sn, Ti, Fe, Sb, Cr and Mo and may have a thickness of 1 to 20 탆, Thickness.

The first bonding layer 740 and the second bonding layer 750 may be disposed between the thermoelectric material layer 710 and the first plated layer 720 and between the thermoelectric material layer 710 and the second plated layer 730 . At this time, the first bonding layer 740 and the second bonding layer 750 may include Te.

The Te content from the center face of the thermoelectric material layer 710 to the interface between the thermoelectric material layer 710 and the first bonding layer 740 is higher than the Bi content, The Te content up to the interface between the layer 710 and the second bonding layer 750 is higher than the Bi content. The Te content from the center face of the thermoelectric material layer 710 to the interface between the thermoelectric material layer 710 and the first bonding layer 740 or the Te content from the center face of the thermoelectric material layer 710, The Te content to the interface between the second bonding layer 750 may be 0.8 to 1 times the Te content of the center face of the thermoelectric material layer 710.

At this time, the pair of the P-type thermoelectric legs 130 and the N-type thermoelectric legs 140 may have the same shape and volume, or may have different shapes and volumes. Since the electrical conduction characteristics of the P-type thermoelectric leg 130 and the N-type thermoelectric leg 140 are different from each other, the height or the cross-sectional area of the N-type thermoelectric leg 140 may be set to a height or a cross- May be formed differently.

The performance of a thermoelectric device according to an embodiment of the present invention can be represented by a Gebeck index. The whiteness index (ZT) can be expressed by Equation (1).

[Equation 1]

Here, α is the Seebeck coefficient [V / K], σ is the electric conductivity [S / m], and α2σ is the power factor (W / mK2). T is the temperature, and k is the thermal conductivity [W / mK]. k can be expressed as a · cp · ρ, where a is the thermal diffusivity [cm2 / S], cp is the specific heat [J / gK], and ρ is the density [g / cm3].

In order to obtain the whiteness index of the thermoelectric element, the Z value (V / K) is measured using a Z meter, and the Zebek index (ZT) can be calculated using the measured Z value.

Here, the lower electrode 120 disposed between the lower substrate 110 and the P-type thermoelectric leg 130 and the N-type thermoelectric leg 140, and the upper substrate 160 and the P- The upper electrode 150 disposed between the n-type thermoelectric leg 130 and the n-type thermoelectric leg 140 includes at least one of copper (Cu), silver (Ag), and nickel (Ni) Thickness.

If the thickness of the lower electrode 120 or the upper electrode 150 is less than 0.01 mm, the function as an electrode may be deteriorated and the electric conduction performance may be lowered. If the thickness is more than 0.3 mm, .

The lower substrate 110 and the upper substrate 160, which are opposed to each other, may be an insulating substrate or a metal substrate.

The insulating substrate may be an alumina substrate or a polymer resin substrate having flexibility. The flexible polymer resin substrate having flexibility has high permeability such as polyimide (PI), polystyrene (PS), polymethyl methacrylate (PMMA), cyclic olefin copoly (COC), polyethylene terephthalate (PET) Plastic, and the like.

The metal substrate may include Cu, a Cu alloy, or a Cu-Al alloy, and the thickness thereof may be 0.1 mm to 0.5 mm. When the thickness of the metal substrate is less than 0.1 mm or exceeds 0.5 mm, the heat radiation characteristic or the thermal conductivity may become excessively high, so that the reliability of the thermoelectric device may be deteriorated.

In the case where the lower substrate 110 and the upper substrate 160 are metal substrates, a gap between the lower substrate 110 and the lower electrode 120 and between the upper substrate 160 and the upper electrode 150 The dielectric layer 170 may be further disposed.

The dielectric layer 170 includes a material having a thermal conductivity of 5 to 10 W / K, and may be formed to a thickness of 0.01 mm to 0.15 mm. If the thickness of the dielectric layer 170 is less than 0.01 mm, the insulation efficiency or withstanding voltage characteristics may be deteriorated. If the thickness exceeds 0.15 mm, the thermal conductivity may be lowered and the thermal efficiency may be lowered.

At this time, the sizes of the lower substrate 110 and the upper substrate 160 may be different. For example, the volume, thickness, or area of one of the lower substrate 110 and the upper substrate 160 may be greater than the other volume, thickness, or area. Thus, the heat absorption performance or the heat radiation performance of the thermoelectric element can be enhanced.

In addition, a heat radiation pattern, for example, a concavo-convex pattern may be formed on at least one surface of the lower substrate 110 and the upper substrate 160. Thus, the heat radiation performance of the thermoelectric element can be enhanced. When the concavo-convex pattern is formed on the surface contacting the P-type thermoelectric leg 130 or the N-type thermoelectric leg 140, the junction characteristics between the thermoelectric leg and the substrate can be improved.

The thermoelectric module may be applied to a power generating device, a cooling device, a heating device, and the like. Specifically, the thermoelectric module is mainly used for an optical communication module, a sensor, a medical instrument, a measuring instrument, an aerospace industry, a refrigerator, a chiller, a ventilation sheet, a cup holder, a washing machine, a dryer, A power supply, a thermopile, or the like.

Here, an example in which the thermoelectric module is applied to a medical instrument is a PCR (Polymerase Chain Reaction) device. The PCR device is a device for amplifying DNA to determine the DNA sequence and is a device that requires precise temperature control and thermal cycling. For this purpose, a Peltier based thermoelectric element can be applied.

Another example in which the thermoelectric module is applied to a medical instrument is a photodetector. Here, the photodetector includes an infrared / ultraviolet detector, a CCD (Charge Coupled Device) sensor, an X-ray detector, and a TTRS (Thermoelectric Thermal Reference Source). A Peltier-based thermoelectric device can be applied for cooling the photodetector. Thus, it is possible to prevent a wavelength change, an output drop, and a resolution degradation due to a temperature rise inside the photodetector.

Another example in which the thermoelectric module is applied to a medical instrument includes a field of immunoassay, a field of in vitro diagnostics, a general temperature control and cooling system, Chiller System, and Blood / Plasma Temperature Control. Thus, precise temperature control is possible.

Another example in which the thermoelectric module is applied to a medical device is an artificial heart. Thus, power can be supplied to the artificial heart.

Examples of applications of the thermoelectric module to the aerospace industry include star tracking systems, thermal imaging cameras, infrared / ultraviolet detectors, CCD sensors, Hubble Space Telescopes, and TTRS. Accordingly, the temperature of the image sensor can be maintained.

Other examples in which the thermoelectric module is applied to the aerospace industry include cooling devices, heaters, power generation devices, and the like.

In addition, the thermoelectric module can be applied to other industries for power generation, cooling, and heating.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims It can be understood that

Claims (12)

A thermoelectric powder,
The thermoelectric powder is a thermally-
A plurality of first powders arranged in a horizontal direction and in a plate-like blade shape; And
And a plurality of second powders different in shape from the first powders,
And the second powders are contained in an amount of 5 vol% or less with respect to the entire thermoelectric powder. The method according to claim 1,
Wherein the first powder arranged in the horizontal direction among the first powders is 95 vol% or more with respect to the entire first powders. The method according to claim 1,
And the second powders are contained in an amount of not more than 3 vol% with respect to the entire thermoelectric powder. The method according to claim 1,
And the second powders are contained in an amount of not more than 1 volume% with respect to the entire thermoelectric powder. 5. The method according to any one of claims 1 to 4,
Wherein the size of the first powder differs from the size of the second powder. 6. The method of claim 5,
And the second powder is formed in a ball shape. The method according to claim 6,
And the second powder has a particle diameter of 300 mu m to 1100 mu m. The method according to claim 6,
And the second powder has an average particle diameter of 650um to 670um. The method according to claim 1,
Wherein a void in the thermoselective body is 5% or less with respect to the total area. A lower substrate;
An upper substrate disposed on the lower substrate;
A plurality of legs disposed between the lower substrate and the upper substrate;
A lower electrode connecting the leg and the lower substrate; And
And an upper electrode connecting the leg and the lower substrate,
Wherein the leg comprises a thermoelectric powder,
The thermoelectric powder is a thermally-
A plurality of first powders in a plate-like blade shape arranged in a horizontal direction; And
And a plurality of second powders different in shape from the first powders,
Wherein the second powders are contained in an amount of 5 vol% or less with respect to the entire thermoelectric powder. 11. The method of claim 10,
Wherein the first powder arranged in the horizontal direction among the first powders is 95 vol% or more with respect to the entire first powders. 11. The method of claim 10,
Wherein a void in the thermoselective body is 5% or less of the total area.

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